Films from PVA modified with nonhydrolyzable anionic comonomers

ABSTRACT

A PVA film modified with anionic comonomers is provided for use as a water-soluble seal or pouch for alkaline or borate-containing cleaning compositions. The films comprise copolymers of 90-100% hydrolyzed vinyl alcohol with a nonhydrolyzable anionic comonomer, and have molecular weights characterized by a viscosity range of 4-35 cPs. The films are resistant to insolubilization caused by alkaline or borate-containing additives, are storage stable over a wide range of temperature and humidity storage conditions, rapidly and fully solubilize in a wash solution, and do not significantly impair cleaning performance of an additive enclosed within.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Continuation-in-Part of Ser. No. 07/050,260, filed May 14,1987, now U.S. Pat. No. 4,747,976 entitled "PVA Films withNonhydrolyzable Comonomers", assigned to the same assignee as theinvention herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to free-standing water-soluble polymeric films andmore particularly to such films in the form of pouches and containingalkaline or borate-containing cleaning compositions.

2. Description of Related Art

A great deal of art relates to water-soluble polymeric films includingpolyvinyl alcohol. Much of the art has been addressed to the problem ofpackaging materials in such water-soluble films. As used herein, theterm film describes a continuous, homogenous, dimensionally stablepolymer having a small thickness in relation to area. As also usedherein "polymer" means a macromolecule made up of a plurality ofchemical subunits (monomers). The monomers may be identical orchemically similar, or may be of several different types. Unless a morespecific term is used, "polymer" will be taken to include hetero- andhomo-polymers, and random, alternating, block and graft copolymers."Copolymer" will be used to specifically refer to those polymers madefrom two different repeating chemical monomers. An effectivewater-soluble package would simplify dispensing, dispersing, slurrying,or dissolving materials contained within, as the entire package could bedumped into a mixing vessel without the need to pour out the contents.Water-soluble film packages could be used where the contents are toxicor messy, where the contents must be accurately measured, or maintainedin an isolated environment, and further allow delivery of materialswhich are only metastable when combined, and which would ordinarilyseparate during storage. Soluble pre-measured pouches aid convenience ofconsumer use in a variety of applications, particularly those involvingcleaning compositions. Such cleaning compositions may include, forexample, detergent formulations for ware-washing applications, detergentcompositions for washing of clothes, and laundry additives such asperoxygen bleaches, fabric softeners, enzymes and related products.Pouching cleaning compositions presents the added problem ofhighly-alkaline contents which can interact with polyvinyl alcohol (PVA)films which surprisingly severely reduces their solubility, strength, orboth. The presence of borate in cleaning compositions (e.g. thosecontaining perborate bleaches) can cause cross-linking of the PVA,reducing its solubility in water. The prior art has attempted tomimimize the deleterious effects of borate ions by including a boratescavenger such as sorbitol in the film formulation.

The use of PVA films to contain cleaning compositions is furtherhampered by variations in solubility caused by the range of watertemperatures employed. PVA films of the art generally exhibit varyingsolubilities in hot (above about 49° C.), warm (about 35° C.) and cold(below about 21° C.) water, depending on the residual acetate content.In addition to the need for rapid film solubility under a variety ofwash conditions, the films must be stable over typical storage periodsand under a variety of environmental conditions. For example, a filmpouch containing a detergent product my be stored under conditions ofmoderate temperature and humidity, under high temperature and lowhumidity, or high temperature and high humidity. The latter is notuncommon in certain areas of the Southeastern United States. In highhumidity conditions, water can penetrate the film, and if an alkalinedetergent is present, can have an adverse impact on the film'sintegrity. One approach to correcting this problem has been to modify orrestrict the amount of alkaline material within the pouch. This can,however, have an adverse impact on the cleaning performance. Anotherproblem with water-soluble PVA film pouches for fabric laundering is theadverse effect of the PVA on cleaning performance.

U.S. Pat. No. 3,892,905 issued to Albert discloses a cold-water solublefilm which may be useful when packaging detergent, Albert, however, doesnot solve the problem of insolubilization due to alkaline orborate-containing compounds. Great Britain patent application 2,090,603,to Sonenstein, describes a packaging film having both hot and cold-watersolubility and made from a blend of polyvinyl alcohol and polyacrylicacid. The acrylic acid polymer acts as an alkalinity scavenger, but asthe acrylic acids become neutralized, the blend loses its resistance toalkalinity and becomes brittle. The polymers of Sonenstein are notcompatible, and preferably are made separately, then blended. This meansan extra process step, and the blend may result in a poor quality film.Dunlop, Jr., U.S. Pat. No. 3,198,740 shows a cold-water solubledetergent packet of PVA containing a granular detergent having ahydrated salt to maintain moisture in the film, but without apparentbenefit to solubility. U.S. Pat. No. 4,115,292 issued to Richardson etal shows compositions with enzymes embedded in water-soluble PVA strips,which are in turn encased in a water-soluble film pouch which may bePVA. Lowell et al, U.S. Pat. No. 3,005,809 describes copolymers of PVAwith 4-10 mole percent of a crotonic acid salt from which films can bemade to package neutral, chlorine-liberating compounds. Lowell et aldoes not teach or suggest any solubility benefits when the films areused to package alkaline or borate-containing detergent compositions.

Inskip, U.S. Pat. No. 3,689,469 describes a hot-water soluble copolymerof about 100% hydrolyzed vinyl acetate and about 2 to 6 weight percentmethyl methacrylate, and is made to minimize the presence of acidgroups. The copolymer can be hydrolyzed using a basic catalyst to formlactone groups, and has utility as a textile yarn warp-sizing agentNeher, U.S. Pat. No. 2,328,922 and Kenyon, U.S. Pat. No. 2,403,004disclose copolymers of vinyl acetate and acrylic esters, and teachlactone formation to obtain insoluble films. Takigawa, U.S. Pat. No.3,409,598 teaches a process for formation of a water-soluble films usinga copolymer of vinyl acetate and an acrylic ester. U.S. Pat. Nos.3,513,142 issued to Blumberg, and 4,155,893 issued to Fujimoto disclosecopolymers of vinyl acetate and a carboxylic ester-containing comonomer.Schulz et al, U.S. Pat. No. 4,557,852 describes polymeric sheets whichdo not include polyvinyl alcohol, but are addition polymers containinghigh amounts of water-insoluble monomers such as alkyl acrylates andwater-soluble anionic monomers such as acrylic salts, and is directed tomaintaining flexibility of the sheet during storage. Kaufmann et al,U.S. Pat. No. 4,626,372 discloses a PVA film having a polyhydroxycompound which reacts with borate to afford the film good solubility inthe presence of borate. Roullet et al, U.S. Pat. No. 4,544,698,describes a PVA and latex combination used as gas-tight moistureresistant coating agents for packaging materials. The latex may includeacrylates or methacrylates and vinylidene polychloride polymerized withacrylate, methacrylate or itaconic acid.

The problem of enclosing an alkaline or borate-containing laundryproduct in a water-soluble pouch, which is sufficiently strong for acommercial product, remains storage stable for durations and underenvironmental conditions typically encountered, and remainswater-soluble over a range of wash/rinse temperatures typicallyencountered in the household, has not been successfully resolved.Accordingly, it is an object of the present invention to provide awater-soluble film and process for making the same which retains itswater solubility in the presence of an alkaline or a borate-containing.[.cleaning.]. composition.

It is another object of the present invention to provide a free-standingfilm which is water-soluble and stable during storage over a wide rangeof temperatures and humidities.

It is another object of the present invention to provide a water-solublefilm which can be used to package a cleaning composition and does nothave deleterious effects on the performance thereof.

It is yet another object of the present invention to provide adissolvable laundry additive packet which can be used with alkaline orborate-containing laundry additives.

It is another object to provide a pre-measured, conveniently packageddose of cleaning composition which is easily stored, handled anddelivered to a washing machine, and will rapidly release the cleaningcomposition into the wash liquor.

SUMMARY OF THE PRESENT INVENTION

In one embodiment, the present invention is a film formed from a resinhaving a vinyl acetate monomer copolymerized with a comonomer selectedfrom a hereinafter defined group. After such copolymerization, and aconversion step, the comonomers are characterized by the presence of ananionic species, and are hereinafter referred to as "nonhydrolyzable"comonomers. The conversion step comprises at least a base catalyzedsaponification step, in an organic solvent, to convert residual acetategroups to alcohols, and to produce the anionic species characterizingthe nonhydrolyzable comonomer. In some cases, the presence of adjacentalcohols and carboxylic esters causes the formation of internal lactonerings. By the additional conversion step of subsequently treating theresin with a base, the lactones can also be convened to the anionicform, resulting in an anionic resin from which a film can be made. Thislatter step is a hydrolysis step. It has been surprisingly found that byselecting the type and content of comonomer, the molecular weight of thePVA resin, and the degrees of hydrolysis of the vinyl acetate,lactonization and ionomer content, and depending on the type of baseused to neutralize the copolymer, a film can be made which exhibitsrelatively temperature-independent water solubility, and is not renderedinsoluble by alkaline or borate-containing .[.detergent.]. compositions.Further, the film is sufficiently strong to be formed into afree-standing pouch which may be used to package cleaning compositions,particularly alkaline or orate-containing cleaning compositions. Thefilm is resistant to insolubilization caused by high humidity storageconditions, hence is stable over a typical storage shelf life. The filmscan be produced from a single polymer solution, without the need formaking separate polymer solutions, which may be incompatible when mixedfor film production. In a second aspect of the present invention, thetrims are formed into pouches and are used as soluble delivery), meansfor cleaning compositions. Such cleaning compositions include, but arenot limited to dry granular, liquid and mulled detergent compositions,bleaches, fabric softeners, dishwashing detergents, combinationsthereof, and other compositions for improving the aesthetics, feel,sanitation or cleanliness of fabrics or wares. The invention isparticularly well suited for containing detergent mulls such as thosedescribed in European pub lashed patent application No. 0,158,464, filedMarch 21, 1985, entitled "Low-temperature effective detergentcompositions and delivery systems therefor", and 0,234,867, filedFebruary 19, 1987, entitled "Concentrated non-phosphate detergent pastecompositions", both of which are signed to the same assignee as thepresent invention, the specifications of which are incorporated hereinby reference. These mulls may be highly viscous gels or pastes andinclude relatively high concentrations of nonionic surfactants foreffective removal of oily soils. The mulls are formulated to havealkaline detergent builders which aid in particulate soil removal, andare formulated to provide optimum cleaning power, not for ease ofdelivery. The preferred delivery method, both for convenience andaccuracy, is to include a pre-measured amount of the mull within thewater-soluble pouch of the present invention.

It is therefore an advantage of the present invention thathigh-surfactant, high-builder detergent mulls can be convenientlypackaged, stored and delivered.

It is another advantage of the present invention that the films used topackage laundry additives remain soluble over the entire range oftypical wash temperatures and times.

It is another advantage that the films of the present invention willretain their solubility in contact with alkaline or borate-containingdetergents.

It is yet another advantage that the films can be made from a singlepolymer resin solution.

It is still another advantage of the present invention that the filmsand film pouches containing detergent remain storage stable over a broadrange of environmental conditions.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In a first embodiment, the present invention comprises a free-standingfilm of a vinyl acetate monomer copolymerized with a comonomer which isconverted to yield the nonhydrolyzable comonomer containing an anionicspecies. Preferably, the anionic species characterizing thenonhydrolyzable comonomer is a carboxylate or sulfonate. Residualacetate groups commonly found in PVA resins are susceptible to alkalinehydrolysis when the resin, or a film made therefrom is exposed to asource of alkalinity. As used herein, the term nonhydrolyzable comonomeris defined to include those repeating units in a PVA copolymer notnormally susceptible to hydrolysis by such sources of alkalinity. Thenonhydrolyzable comonomers are characterized by the presence of ananionic group, and may be derived from carboxylic acids and saltsthereof, carboxylic esters, amides, imides, acyl halides, anhydrides andsulfonates, and impart a degree of water solubility to the resin. Thiswater solubility of the resin should be such that films producedtherefrom, having a thickness between about 1 to 5 mils, will disperseand substantially dissolve in 70°-130° F. (21°-54° C.) water in lessthan about fifteen minutes, preferably less than about five minutes.Subsequent to copolymerization, the nonhydrolyzable comonomer resultsfrom the conversion step(s) of, saponification (which also hydrolyzesacetate groups of the polymer to alcohols), or saponification followedby alkaline hydrolysis. The latter hydrolysis step is used when thecomonomer is such that lactones are formed as a result of thesaponification step. As used herein, the term saponification includeseither a base-catalyzed hydrolysis in an organic solvent, or a basecatalyzed hydrolysis in an organic solvent followed by theneutralization of excess base and removal of solvent. Preferred bases tocatalyze the saponification are the alkali metal hydroxides, includingsodium and potassium hydroxide. The organic solvent need not beexclusively organic solvent, but may include some water. Also as usedherein, hydrolysis refers to the conversion, usually in a predominatelyaqueous medium, of a neutral molecule, (e.g. a lactone) to an anionicform, by a source of alkalinity. The presence of adjacent alcohols andcarboxylic esters causes internal lactonization of the copolymer resin,but in the presence of a base such as an alkali metal hydroxide, thelactone rings open to form anionic groups, i.e., the salts of theresulting carboxylic acids. Depending on the degree of hydrolysis of thepolyvinyl alcohol, the type and percent nonhydrolyzable comonomercontent, the degree of lactone conversion, and the type of base used inthe hydrolysis step, the resulting resin can be formulated to exhibitvarying degrees of water solubility and desired stabilitycharacteristics. The anionic groups may be formed during resin or filmproduction, or after film formation. Films can be made with theinventive resin as is known in the art, for example, by solution castingor extrusion, and may be used to pouch gel or mull detergentcompositions. Such mulls include detergent builders containingrelatively high levels of nonionic surfactants to yield superior oilysoil cleaning performance.

A second embodiment of the present invention comprises a film, made asdescribed in the first embodiment, and fabricated into a pouch.Contained within is a cleaning composition which preferably is a highlyviscous, gel or paste detergent composition containing at least onenonionic surfactant and an alkaline builder.

Copolymeric Resins

Polyvinyl alcohol (PVA) resin is widely used as a film forming material,and has good strength and water solubility characteristics. Twoparameters significantly affecting PVA solubility are molecular weightand degree of hydrolysis. Commercially available films range in weightaverage molecular weight from about 10,000 to 100,000 g/mole. Percenthydrolysis of such commercial PVA films is generally about 70% to 100%.Because PVA is made by polymerizing vinyl acetate and subsequentlyhydrolyzing the resin, PVA can and typically does include residualacetates. The term "polyvinyl alcohol" thus includes vinyl alcohol andvinyl acetate copolymers. For solubility purposes, a high degree ofhydrolysis, e.g., 95% renders the film relatively slowly soluble inwater. Lower degrees of hydrolysis, e.g. 80-95%, improve solubilityrates. In an alkaline environment however, these films become relativelyinsoluble due to the continued hydrolysis of the partially hydrolyzedfilm. Higher molecular weight films generally exhibit the bestmechanical properties, e.g., impact strength, however solubility ratesmay be reduced.

It has been surprisingly found that films of the present invention,which are capable of being made into pouches, are storage stable,rapidly soluble over a wide temperature range and are not deleterious tocleaning performance, can be produced from vinyl acetate copolymerizedwith about 2-6 mole percent of s comonomer, to an extent to yield aresin with a molecular weight characterized by s viscosity of betweenabout 4 to 35 cPs as measured in a 4% solution at 25° C., the resinbeing saponified such that there are 0-10% residual acetate groups, andthe comonomers being selected such that subsequent to polymerization,they are converted to nonhydrolyzable comonomers having an anioniccharge. As used herein, unless otherwise noted, the resin viscosity ismeasured after copolymerization and saponification, but before anyfurther treatment of the resin. Mole percentage of comonomer is ameasure of the ratio of the number of moles of comonomer to the numberof moles of vinyl acetate plus comonomer. Preferably the resin viscosityshould be in the range of between about 4-35 cPs, and the molepercentage nonhydrolyzable comonomer is about 1-6 percent. Generally, itis desirable to increase the percentage of nonhydrolyzable comonomer asresin viscosity increases, up to the limit of the range. The mostpreferred nonhydrolyzable comonomer is that which results from theconversion of the methyl acrylate comonomer. The most preferred molepercentage of this nonhydrolyzable anionic comonomer is 3-5%, and it isfurther most preferred that the resulting resin have a viscosity ofabout 10-20 cPs.

The comonomers which, when copolymerized with vinyl acetate andconverted, result in the nonhydrolyzable comonomers having an anionicspecies, include carboxylic acids and salts thereof, carboxylic esters,amides, imides, acyl halides, anhydrides and sulfonates. Examples ofsuitable comonomers include unsaturated acids such as acrylic,methacrylic, cis 2-butenoic, 3-butenoic, cinnamic, phenylcinnamic,pentenoic, methylene malonic, the alkali metal and ammonium salesthereof and the acyl halide derivatives thereof; unsaturated esters,amides, and acyl halides of the following structure I: ##STR1## whereinR₁, R₂ and R₃ are H, or alkyl, aryl or hydroxyalkyl groups, n is 0 or 1,and X is --CO₂ R₄, --C(O)NR₄ R₅ or --COY (wherein R₄ is H, or an alkyl,aryl, alkenyl, hydroxyalkyl, oxyalkyl or cyanoalkyl group, R₅ is H or analkyl, aryl or hydroxyalkyl group, and Y is a halide); unsaturateddiacids and their stereoisomers of the following structure II: ##STR2##wherein p and q are integers from 0-5, R₆ and R₇ are H, or alkyl or arylgroups, and alkali metal and ammonium salts thereof; anhydrides, acyclicand cyclic esters, amides and imides derived from structure II;unsaturated sulfonic acids and derivatives thereof, and mixturesthereof.

Most suitable comonomers include acrylic acid, methacrylic acid,methylene malonic acid, methyl acrylate, methyl methacrylate,acrylamide, maleic and itaconic acid anhydrides, methyl esters of maleicand itaconic acids, vinyl sulfonate, and mixtures thereof. Conversion ofthe comonomer to the anionic, nonhydrolyzable comonomer is accomplishedby saponification as defined hereinbefore.

Some comonomers that are carboxylic acid derivatives, e.g., methylacrylate and methyl methacrylate, yield lactones on saponification,owing to the presence of adjacent carboxylic esters and alcohols. It hasbeen further surprisingly found that films produced from such lactonizedresins do not have acceptable solubility characteristics. For suchresins the conversion to anionic form requires alkaline hydrolysisfollowing saponification. The alkaline material used to convert lactonesto anionic form may be added before, during or after film production.Operable alkaline materials include but are not limited to alkali metaland alkaline earth metal hydroxides, particularly sodium, lithium andpotassium hydroxide, and quaternary ammonium hydroxides, particularlytetraethanol and tetraethyl ammonium hydroxides. Depending on thealkaline material selected, the character of the resulting film can bealtered somewhat. For example, solubility of the film is greatest whenlithium hydroxide is employed, followed by the sodium, potassium, andquaternary ammonium hydroxides. Film strength is greatest when thequaternary ammonium compounds are used. The alkaline material is addedin an amount sufficient to attain the desired mole percentagenonhydrolyzable comonomer, i.e., about 1-6 mole percent.

Conversion of the lactone to anionic form may occur as part of the resinor trim production process, or after the film has been made but beforeit is intended to dissolve in water. The introduction of a cleaningcomposition to the film will result in a degree of anion formation ifthe cleaning composition is sufficiently alkaline.

Other Film Components

The following components are also present in the films of the presentinvention, and may be added to the resin during film production. Aplasticizer is added to the resin to plasticize the copolymeric resinand allow film formation therefrom. Generally any plasticizer known inthe art for use with PVA resins will function with the presentinvention. Preferred are aliphatic polyols, especially ethylene glycol,propylene glycol, glycerol, trimethylolpropane, polyethylene glycol, andmixtures thereof. Particularly preferred is a mixture of polyethyleneglycol having a molecular weight of about 200-400 g/mole, and glycerol.The total plasticizer content is about 0 to 45% by weight of the filmcomposition, preferably about 15 to 30 wt % of the film.

A surfactant may be added to the resin mixture to aid in film productionby reducing foaming and helping to ensure dispersion and wetting of thecomposition ingredients. Preferred for this purpose are ethoxylatedaliphatic alcohols and ethoxylated alkylphenols. The surfactant may beadded in tn amount of from 0% to about 1.0%, preferably from about 0.01%to 0.05%.

To improve solubility of the film in contact with borate-containingadditives a borate scavenger may be added. The borate scavenger ispreferably a polyhydroxy compound (PHC) capable of binding to the borateto form a borate-PHC complex. A number of PHC compounds are known in theart to complex with borate such as sorbitol, mannitol, catechol andpentaerythritol. Sorbitol is preferred, and may be added in an amount offrom 0 to about 30%, preferably from about 5 to 20%. A more detaileddisclosure of the use of polyhydroxy borate scavengers can be found inU.S. Pat. No. 4,626,372 issued to Kaufmann et al and assigned to thesame assignee as the present invention, the disclosure of which isincorporated herein by reference.

Other film additives as known in the art may be included by mixing withthe resin. These include antioxidants, release agents, antiblockingagents, and antifoamers, all of which are added in mounts sufficient toperform their intended function as known in the art and generallybetween 0 and about 1% by weight. Film thickness may vary from about 1.0to 5.0 mils, preferably about 1.5 to 2.5 mils.

In a second embodiment, the films are used in combination with liquid,solid, granular, paste or mull cleaning compositions to result in apre-measured water-soluble packet for cleaning purposes. The cleaningcomposition may advantageously contain relatively high levels ofnonionic surfactants and/or alkaline builders for superior cleaningperformance, and/or borate-releasing compounds to provide oxidizingpower effective against organic stains. The films of the presentinvention retain their desired solubility, strength and stabilitycharacteristics despite the presence of such alkaline builders orborate, which render ordinary PVA films insoluble, unstable or both. Thealkaline cleaning compositions are generally defined as those whichgenerate a pH of greater than about 8 when dissolved to a level of about1% in an aqueous medium. Borate-containing cleaning compositions aregenerally defined as those yielding a borate ion concentration, inwater, of greater than about 2.0×10⁻⁴ M. A more detailed description ofan example of I detergent mull for which the films of the presentinvention are particularly adapted for delivering can be found in thepreviously described European application Nos. 0,158,464, and 0,234,867.

The amounts of builders and surfactants which can be included can varyconsiderably depending on the nature of the builders, the final desiredviscosity and the amount of water added to the surfactant system. Otheradditives commonly found in detergent compositions can be included inthe formulations herein. These include but are not limited to additionalsurfactant, fluorescent whitening agents, oxidants, corrosion inhibitingagents, anti-redeposition agents, enzymes, fabric softeners, perfumes,dyes and pigments. The detergent composition herein may includephosphate or nonphosphate builders.

The following nonlimiting examples are provided to further illustratethe present invention.

EXAMPLE A

A copolymeric resin was made by copolymerizing vinyl acetate and methylacrylate to yield about 30 g of the copolymer having a 20,000-25,000g/mole weight average molccular weight (with an approximate viscosity of6 cPs) and 4.5 mole percent methyl acrylate. The resin was saponified toconvert 100% of the acetate groups to alcohols and to cause theformation of lactones. The resin had an initial lactone mole percentageof about 4.5%, and a melting temperature of 206° C. About 30 g of theresin was added to about 190 g of deionized water, and stirred todisperse. About 4 g of a plasticizer, plus about 2 g of a boratescavenger were added to the resin and small quantities (under about0.5%) of an antiblocking/release agent and an antioxidant were added.The dispersion was heated for about two hours at 60°-70° C. to fullydissolve the resin. To this solution sufficient NaOH was added, withheating, to hydrolyze about 1 to 4 mole percent of the lactone groups toanionic form.

The solution was heated for an additional five hours at 60°-70° C. tocomplete the hydrolysis, and was then slowly cooled to about 23° C. anddeaerated. The solution was cast on a stainless steel plate using a filmapplicator with a 0.2 cm clearance. The resulting film was dried at 61°C. for about 30 minutes, cooled to room temperature, and removed fromthe plate. This procedure yielded a film about 2.5 mils thick, andcontaining about 70.3% copolymer, 14.3% plasticizer, 7.2% boratescavenger, and 8.2% water.

All of the solubility data were obtained by placing the film in a testdevice (a 35 mm format slide having a 3 cm×4.5 cm aperture) in a 600 mlbeaker containing about 325 ml of deionized water. Washing machineagitation was simulated by stirring the test solution with a magneticstirrer at a speed sufficient to result in a vortex extending downwardfor about 20% of the solution depth. In simulations involving borate,Na₂ B₄ O₇ was added to the water to result in a borate concentration ofabout 1.7×10⁻³ M, and the pH was adjusted to 10.7 with sodiumcarbonate/bicarbonate. Solubilities of films stored in contact withalkaline cleaning products were determined after the films were removedfrom contact with the cleaning products and any residual cleaningproduct adhering to the films was wiped off. Film solubilities werevisually evaluated as percentage film residue remaining after 300seconds in the stirred beaker. Separate studies showed that if the filmfully dissolved after 300 seconds in the beaker, no undissolved filmresidue would be expected from pouched cleaning products in actual useconditions.

EXAMPLES B-I

Example B was made as described for Example A, with the copolymericresin polymerized to have a molecular weight corresponding to about 10cPs instead of the 6 cPs. Examples C, D and E were made as described forExample A, but were polymerized to have viscosities of 14 cPs, 17 cPsand 30 cPs, respectively. Example F was made as Example A with methylmethacrylate instead of methyl acrylate, and with a viscosity of about15 cPs. Example G was made by copolymerizing vinyl acetate and maleicacrylate, and had a viscosity of 17 cPs. Example G did not, however,require the subsequent alkaline hydrolysis step of Example A, as thecomonomer of Example G was already in anionic form. Examples H and I areprior art polymers of 88% hydrolyzed PVA.

EXPERIMENTAL RESULTS

I. Effects of Resin Viscosity and Copolymer Type and Percent on AlkalineStability

The alkaline stability of films using various PVA copolymer resins wasobserved for the following films. Long term film storage in contact withan alkaline detergent was simulated by storing the films in a saturatedNaCl solution with the pH adjusted with NaOH to about 12. Dissolutionwas observed after storage times of 2, 4, 8 and 24 hours in thesolution. This test, termed an "accelerated test", simulated in 2 and 4hours the effect of actual storage for one and two weeks at 32° C./85%RH. The 8 and 24 hour storage conditions simulated prolonged actualstorage at high humidity. Results are given as percent film remainingafter 300 sec in a beaker under the test conditions as outlinedpreviously. Zero percent film remaining indicates desired solubility.The dissolution medium was 21° C. water.

                  TABLE 1                                                         ______________________________________                                                              Mole                                                                          %      Solubility                                       Resin    Comonomer    Resi-  (% Film residue                                  Vis-              Total   dual after 300 sec                                  cosity            Mole    Ace- in 21° C. water)                        Film cPs     Type     %     tate 2     4    8    24.sup.1                     ______________________________________                                        A     6      Acry-    4.5   0    0      0    0   0                                         late.sup.*                                                       B    10      Acry-    4.5   0    0      0    0   0                                         late*                                                            C    14      Acry-    4.5   ≦1                                                                          0      0    0   0                                         late*                                                            D    17      Acry-    4.5   0    0      0    0   0                                         late*                                                            E    30      Acry-    4.5   0    0      0    0   0                                         late*                                                            F    15      Meth-    2.7   0    Trace  0    0   0                                         acry-                                                                         late*                                                            G    17      Maleate  2.3   3-5  0      0    0   0                            H     5      None     --    12   0      50  --                                                                       100                                    I    13      None     --    12   0     100  100  --                           ______________________________________                                         *methyl esters                                                                .sup.1 Hours in accelerated test solution                                

This table illustrates that films A-G which are prepared in accordancewith the present invention, maintain their solubility under extremealkaline storage conditions. Films H and I, which are prior art films ofvinyl alcohol and vinyl acetate, quickly lose their solubility.

II Long-term Stability of Film A with Alkaline Paste Detergent

Pouches of an alkaline paste detergent containing a nonionic surfactant,sodium tripolyphosphate, Na₂ CO₃, silicate, protease, and a fragrancewere prepared using Films D and H. These pouches were exposed to thefollowing storage conditions in a cycling temperature/humidity room, andmonitored for film solubility. The cycling room is designed to cycletemperature and humidity from 21° C./87% RH to 32° C./65% RH and backover a 24 hour period. These conditions simulate actual weatherconditions found in humid regions of the United States.

                  TABLE 2                                                         ______________________________________                                        Solubility (21° C. water)                                              % film Residue After 300 Sec.                                                         Cycling     21° C./50% R.H. 6 weeks +                          Film    Room 8 weeks                                                                              Cycling Room 3 weeks                                      ______________________________________                                        D        0           0                                                        H       80          75                                                        ______________________________________                                    

Table 2 demonstrates that the films of the present invention are notinsolubilized by hot and/or humid environmental conditions, whereas theprior art PVA film (film H) became, for practical purposes, insolubleunder the same conditions.

III. Stability of Film C with Additional Cleaning Products

                  TABLE 3                                                         ______________________________________                                                            Solubility.sup.(1)                                        Product               Film C  Film H                                          ______________________________________                                        Dry Detergent         0       Trace                                           5% Perborate (pH 10.7*)                                                       Dry Bleach            0       25%                                             15% Perborate (pH 11.2*)                                                      Dry Automatic         0       10%                                             Dishwashing Detergent (PH 10.3*)                                              ______________________________________                                         *of a 1% solution                                                             .sup.(1) Percent of film remaining after 300 sec. in 21° C. water      following storage in a cycling room for 4 weeks                          

Table 3 shows the usefulness of the films of the present invention withborate-containing, and highly alkaline additives. It is thought that theanionic nature of the films functions to repel borate anions, and toprevent cross-linking which renders prior art films insoluble.

It has been surprisingly found that molecular weight as represented byviscosity of a 4% polymer solution, and comonomer type and content canimpact the cleaning performance of laundry detergents on certain soils,(e.g., on clay soil). Cleaning performance was evaluated by measuringpercentage soil removal as a change in fabric reflectance. Swatches ofcotton fabric were prepared and stained with BANDY BLACK clay (atrademarked product of the H. C. Spinks Clay Co.), and washed in acommercially available washing machine. Test conditions included 68L of38° C. water at a hardness of 100 ppm (Ca²⁺ and Mg²⁺ in a 3:1 ratio). A1.8 g piece of film and 53.7 g of paste detergent were used in theevaluation.

Reflectance values of the swatches were measured on a Gardnercolorimeter before and after the wash, and the data were analyzed usingthe Kubelka-Munk equation.

IV. Effect of Polymer Solution Viscosity and Anionic NonhydrolyzableComonomer Content on Cleaning Performance

                  TABLE 4                                                         ______________________________________                                              Resin       Mole %                                                            Viscosity.sup.(1)                                                                         Anionic    Cleaning Performance                             Film  cPs         Comonomer  (% Soil Removal)                                 ______________________________________                                        A      6          3.4        92                                               C     14          3.4        90                                               E     30          3.4        97                                               H      5          0          90                                               I     13          0          80                                               ______________________________________                                         .sup.(1) Measured as a 4% aqueous solution at 25° C.              

It is beneficial, for film strength reasons, to have as high a molecularweight (viscosity) as possible. High molecular weight films of the priorart, however result in poor clay soil performance (a 13 cPs prior artfilm yielded about a 10% decrease m cleaning performance over a 5 cPsprior art film). The films of the present invention, however, show onlyslight decreases in cleaning performance as viscosity is increased from6 (film A) to 14 cPs (film C) and 30 cPs (film E). For example, film Eof the present invention, at a resin viscosity of 30 cPs, exhibitsbetter cleaning performance than 13 cPs film (film I) of the prior art.

V. Effect of Anionic Nonhydrolyzable Comonomer Content on InitialSolubility

                  TABLE 5                                                         ______________________________________                                                    Solubility                                                                    (% Film Residue                                                               After 300 Sec.)                                                   Film          4° C./Water                                                                       21° C./Borate                                 ______________________________________                                        B     Anionic      0          0                                               B     Neutral     50         25                                               C     Anionic      0          0                                               C     Neutral     50         25                                               D     Anionic      0          0                                               D     Neutral     100        100                                              ______________________________________                                    

Table 5 shows the neutral copolymer films (e.g. with the comonomer inlactone form) do not dissolve completely in cold or borate-containingwater. When the films are in anionic form, i.e., the lactones areconverted to the anionic comonomer, however, complete initialdissolution is achieved.

VI. Effect of Anionic Nonhydrolyzable Comonomer Content on CleaningPerformance

The degree of anion content in the copolymer films affects the clay-soilremoval efficiency of the paste detergent as well as the initialsolubility exhibited in the previous example. This effect wasdemonstrated by controlling the amount of hydrolysis of lactone groupsof film D to vary the anion content of the resin. Cleaning performancewas measured as described for Table 4, above.

                  TABLE 6                                                         ______________________________________                                        Mole Percent Anionic                                                          Nonhydrolyzable Comonomer                                                                         Percent Soil                                              (Film D)            Removal                                                   ______________________________________                                        3.4                 91                                                        2.3                 90                                                        1.2                 87                                                        0                   84                                                        ______________________________________                                    

Table 6 shows that at a given viscosity level of the of the presentinvention, better clay soil removal can be achieved by increasing theanionic content of the film, which can be controlled by the mount ofcomonomer, and in some cases, by the degree of hydrolysis ofintermediate lactone groups.

While described in terms of the presently preferred embodiments, it isto be understood that such disclosure is not to be interpreted aslimiting. Various modifications and alterations will no doubt occur tothose skilled in the art after having read the above disclosure.Accordingly, it is intended that the appended claims be interpreted ascovering all alterations and modifications as fall within the truespirit and scope of the invention.

What is claimed is:
 1. A water-soluble polymeric film and .[.cleaningcomposition.]. .Iadd.additive .Iaddend.combination comprising(a) awater-soluble film about 1-5 mils thick, formed from a copolymer resinof vinyl alcohol having about 0-10 mole percent residual acetate groupsand about 1-6 mole percent of a nonhydrolyzable anionic comonomerconverted from the group of comonomers consisting of(i) unsaturatedacids .[.such as.]. .Iadd.selected from the group consisting of.Iaddend.acrylic, methacrylic, cis 2-butenoic, 3-butenoic, cinnamic,phenylcinnamic, pentenoic, methylene malonic, the alkali metal andammonium salts thereof and the acyl halide derivatives thereof; (ii)unsaturated esters, amides, and acyl halides of the following structureI: ##STR3## wherein R₁, R₂ and R₃ are H, or alkyl, aryl or hydroxyalkylgroups, n is 0 or 1, and X is .[.[--CO₂ R₄ ].]. --C(O)NR₄ R₅ or --COY(wherein R₄ is H, alkyl, aryl, alkenyl, hydroxyalkyl, oxyalkyl orcyanoalkyl group, R₅ is H or an alkyl, aryl or hydroxyalkyl group, and Yis a halide); or X is CO₂ R₄, wherein R₄ is an alkyl, aryl, alkenyl,hydroxaylkyl, oxyalkyl or cyanoalkyl group; (iii) unsaturated diacidsand their stereoisomers of the following structure II: ##STR4## whereinp and q are integers from 0-5, R₆ and R₇ are H, or alkyl or aryl groups,and alkali metal and ammonium salts thereof; (iv) anhydrides, acyclicand cyclic esters, amides and imides derived from structure II; (v)unsaturated sulfonic acids and derivatives thereof; and (vi) mixturesthereof, the resin being polymerized to an extent to result in a resinviscosity, when dissolved in 25° C. water to a level of about 4% ofbetween about 4-35 cPs, the film including a plasticizing-effectiveamount of a plasticizer, and; (b) an alkaline or borate-containing.[.cleaning.]. composition, said composition being at least partiallyenclosed by the film wherein the film will dissolve when placed in anaqueous medium, freeing the .[.cleaning.]. .Iadd.alkaline orborate-containing .Iaddend.composition.
 2. The combination of claim 1whereinthe nonhydrolyzable anionic comonomer is converted from the groupof comonomers consisting of acrylic acid, methacrylic acid, methylenemalonic acid, methyl acrylate, methyl methacrylate, acrylamide, maleicand itaconic acid anhydrides, methyl esters of maleic and itaconicacids, vinyl sulfonate and mixtures thereof.
 3. The combination of claim1 and further includingabout 0-30 weight percent of a borate scavengerin the polymeric film.
 4. An article for delivering .[.a cleaning.]..Iadd.an additive .Iaddend.composition to .[.a wash liquor.]. .Iadd.anaqueous solution .Iaddend.comprising(a) an alkaline or borate-containingƒcleaning.]. composition at least partially enclosed by .[.the.]..Iadd.a .Iaddend.film wherein the film will dissolve when placed in anaqueous medium, freeing the .[.cleaning.]. composition; and (b) acopolymeric film material having a thickness of .[.cleaning.]..Iadd.between about 1-5 mils, at least partially surrounding the.Iaddend. composition and made from a copolymeric resin produced bycopolymerizing vinyl acetate with about 2-6 mole percent of a comonomerto yield a copolymer resin, subsequently saponifying .Iadd.the.Iaddend.resin to hydrolyze about 90-100 mole percent acetate groups toalcohols, the resulting resin characterized by a viscosity, whendissolved to a level of about 4% in 25° C. water, of between about 4 and35 cPs, and converting sufficient of the comonomer to result in about1-6 mole percent of a nonhydrolyzable comonomer having an anioniccharge, wherein the comonomer is selected from the group consistingof(i) unsaturated acids .[.such as.]. .Iadd.selected from the groupconsisting of .Iaddend.acrylic, methacrylic, cis 2-butenoic, 3-butenoic,cinnamic, phenylcinnamic, pentenoic, methylene malonic, the alkali metaland ammonium salts thereof and the acyl halide derivatives thereof; (ii)unsaturated esters, amides, and acyl halides .[.or.]. .Iadd.of.Iaddend.the following structure I: ##STR5## wherein R₁, R₂ and R₃ areH, or alkyl, aryl or hydroxyalkyl groups, n is 0 or 1, and X is.[.[--CO₂ R₄ ].]. --CO₂ R₄, --C(O)NR₄ R₅ or --COY (wherein R₄ is H, oran alkyl, aryl, alkenyl, hydroxyalkyl, oxyalkyl or cyanoalkyl group, R₅is H or an alkyl, aryl or hydroxyalkyl group, and Y is a halide); or Xis CO₂ R₄, wherein R₄ is an alkyl, aryl, alkenyl, hydroxaylkyl, oxyalkylor cyanoalkyl group; (iii) unsaturated diacids and their stereoisomersof the following structure II: ##STR6## wherein p and q are integersfrom 0-5, R₆ and R₇ are H, or alkyl or aryl groups, and alkali metal andammonium salts thereof; (iv) anhydrides, acyclic and cyclic esters,amides and imides derived from structure II; (v) unsaturated sulfonicacids and derivatives thereof; and (vi) mixtures thereof, the filmincluding a plasticizing-effective amount of a plasticizer;wherein thealkaline borate-containing .[.cleaning.]. composition is at leastpartially enclosed by the film such that the film will dissolve whenplaced in an aqueous medium, .[.frecing.]. .Iadd.freeing .Iaddend.thecomposition.
 5. The article of claim 4 whereinthe comonomer is selectedfrom the group consisting of acrylic acid, methacrylic acid, methylenemalonic acid, methyl acrylate, methyl methacrylate, acrylamide, maleicand itaconic acid anhydrides, methyl esters of maleic and itaconicacids, vinyl sulfonate, and mixtures thereof.
 6. The article of claim 4whereinthe conversion of the comonomer to the nonhydrolyzable comonomeroccurs during the saponification.
 7. The article of claim 4 whereintheconversion of the comonomer to the nonhydrolyzable comonomer furtherincludes a hydrolysis with an alkaline material, following thesaponification.
 8. The article of claim 7 whereinthe alkaline materialis an alkaline-earth metal, alkali-metal, or quaternary ammoniumhydroxide, and mixtures thereof.
 9. The article of claim 7 whereinthealkaline material is .[.included in the.]. .Iadd.a .Iaddend.cleaningcomposition.
 10. In a wash article of the type comprising a washadditive at least partially surrounded by a water-soluble, plasticizedpolyvinyl alcohol film, the improvement comprising(a) making the filmfrom a resin formed by copolymerizing vinyl acetate with about 2-6 molepercent of a comonomer selected from the group consisting of(i) acrylic,methacrylic, cis 2-butenoic, 3- butenoic, cinnamic, phenylcinnamic,pentenoic, and methylene malonic acids, the alkali metal and ammoniumsalts thereof and the acyl halide derivatives thereof; (ii) unsaturatedesters, amides, and acyl halides of the following structure I: ##STR7##wherein R₁, R₂ and R₃ are H, or alkyl, aryl or hydroxyalkyl groups, n is0 or 1, and X is .[.[--CO₂ R₄ ].]. --CO₂ R₄, --C(O)NR₄ R₅ or --COY(wherein R₄ is H, or an alkyl, aryl, alkenyl, hydroxyalkyl, oxyalkyl orcyanoalkyl group, R₅ is H or an alkyl, aryl or hydroxyalkyl group, and Yis a halide); or X is CO₂ R₄, wherein R₄ is an alkyl, aryl, alkenyl,hydroxaylkyl, oxyalkyl or cyanoalkyl group; (iii) unsaturated diacidsand their stereoisomers of the following structure II: ##STR8## whereinp and q are integers from 0-5, R₆ and R₇ are H, or alkyl or aryl groups,and alkali metal and ammonium salts thereof; (iv) anhydrides, acyclicand cyclic esters, amides and imides derived from structure II; (v)unsaturated sulfonic acids and derivatives thereof; and (vi) mixturesthereof, to form a copolymer resin; (b) saponifying the resin tohydrolyze about 90-100 mole percent of acetate groups to alcohols, thecopolymer resin being polymerized to an extent to result in a resinviscosity, when dissolved to a level of 4% in water at 25° C., of about4-35 cPs; and (c) converting sufficient of the comonomer to result inabout 1-6 mole percent of an anionic, nonhydrolyzable comonomer.
 11. Thearticle of claim 10 wherein the comonomer is selected from the groupconsisting of acrylic acid, methacrylic acid, methylene malonic acid,methyl acrylate, methyl methacrylate, acrylamide, maleic and itaconicacid anhydrides, methyl esters of maleic and itaconic acids, vinylsulfonate, and mixtures thereof.
 12. The article of claim 10 whereintheconversion of the comonomer to the nonhydrolyzable comonomer occursduring the saponification.
 13. The article of claim 10 whereintheconversion of the comonomer to the nonhydrolyzable comonomer furtherincludes a hydrolysis with an alkaline material, following thesaponification.
 14. The article of claim 13 whereinthe alkaline materialis an alkaline-earth metal, alkali-metal, or quaternary ammoniumhydroxide, and mixtures thereof.
 15. The article of claim 13 whereinthealkaline material is included in the wash additive.
 16. The article ofclaim 10 and further includingabout 0 to 30 weight percent of a boratescavenger in the film.
 17. A method for introducing .[.a wash.]..Iadd.an alkaline or borate-containing .Iaddend.additive to an aqueous.[.wash.]. solution comprising(a) enclosing .[.a wash.]. .Iadd.analkaline or borate-containing .Iaddend.additive in a sealedwater-soluble copolymeric film material produced by copolymerizing vinylacetate with about 2-6 mole % of a comonomer to yield a copolymer resin,subsequently saponifying the resin to hydrolyze about 90-100 molepercent acetate groups to alcohols, the copolymer resin characterized bya viscosity, when dissolved to a level of about 4% in 25° C. water, ofbetween about 4 to 35 cPs, and converting sufficient of the comonomer toresult in about 1-6 mole percent of a nonhydrolyzable comonomer havingan anionic charge, wherein the comonomer is selected from the groupconsisting of(i) unsaturated acids .[.such as.]. .Iadd.selected from thegroup consisting of .Iaddend.acrylic, methacrylic, cis 2-butenoic,3-butenoic, cinnamic, phenylcinnamic, pentenoic, methylene malonic, thealkali metal and ammonium salts thereof and the acyl halide derivativesthereof; (ii) unsaturated esters, amides, and acyl halides of thefollowing structure I: ##STR9## wherein R₁, R₂ and R₃ are H, or alkyl,aryl or hydroxyalkyl groups, n is 0 or 1, and X is .[.[--CO₂ R₄ ].].--CO₂ R₄, --C(O)NR₄ R₅ or --COY (wherein R₄ is H, or an alkyl, aryl,alkenyl, hydroxyalkyl, oxyalkyl or cyanoalkyl group, R₅ is H or analkyl, aryl or hydroxyalkyl group, and Y is a halide); or X is CO₂ R₄,wherein R₄ is an alkyl, aryl, alkenyl, hydroxyalkyl, oxyalkyl orcyanoalkyl group; (iii) unsaturated diacids and their stereoisomers ofthe following structure II: ##STR10## wherein p and q are integers from0-5, R₆ and R₇ are H, or alkyl or aryl groups, and alkali metal andammonium salts thereof; (iv) anhydrides, acyclic and cyclic esters,amides and imides derived from structure II; (v) unsaturated sulfonicacids and derivatives thereof; and (vi) mixtures thereof; and (b)contacting the copolymeric material plus additive with an aqueous.[.wash.]. solution for a sufficient time .[.Lo.]. .Iadd.to.Iaddend.dissolve the polymeric material and disperse the additivecontained therein.
 18. The method of claim 17 wherein the comonomer isselected from the group consisting of acrylic acid, methacrylic acid,methylene malonic acid, methyl acrylate, methyl methacrylate,acrylamide, maleic and itaconic acid anhydrides, methyl esters of maleicand itaconic acids, vinyl sulfonate, and mixtures thereof.
 19. Themethod of claim 17 whereinthe conversion of the comonomer to thenonhydrolyzable comonomer occurs during the saponification.
 20. Themethod of claim 17 whereinthe conversion of the comonomer to thenonhydrolyzable comonomer further includes a hydrolysis with an alkalinematerial, following the saponification.
 21. The method of claim 20whereinthe alkaline material is an alkaline-earth metal, alkali-metal,or quaternary ammonium hydroxide, and mixtures thereof.
 22. The methodof claim 20 whereinthe alkaline material is included in the .[.wash.].additive.
 23. The method of claim 17 and further includingadding about 0to 30 weight percent of a borate scavenger in the film.